Patent GB-569647-A (GB)
Title: Improvements in or relating to photographic colour processes
IPC: G03C7/327
Filed: 1943-10-29
Abstract: Dye intermediates have the general formula <FORM:0569647/IV/1> where R1 and R2 are the same or different and represent H, or alkyl, cycloalkyl, or substituted alkyl groups (e.g. methyl, ethyl, dodecyl, cyclohexyl, or benzyl groups, which may contain substituents such as halogen atoms or ether, thioether, amide or sulphone groups) or one of them, together with the group X, forms part of a heterocyclic nucleus, X is a hydrocarbon radical or a hydrocarbon radical containing an ether linkage or any other group substantially preventing coupling in the 2-position, Y is H or a replaceable atom or group permitting azo coupling in the 4-position (e.g. a halogen atom or a free SO3H or COOH group), and A is a benzene nucleus which may be substituted by hydrocarbon radicals, ether groups, halogen atoms, or SO3H or COOH groups in the 5, 6, 7 or 8 positions, and may have a molecular weight of at least 300.  Intermediates of high molecular weight may be produced by substituting the amino group with an amino-substituted substituent and acylating the external amino group with a high molecular weight acid (including polymeric and poly acids and derivatives thereof, e.g. halides and esters); derivatives of stearic, phthalic, octadecylsulphonic and polyacrylic acids and heteropolymers of maleic anhydride with vinyl compounds may be used. The original amino group may be directly alkylated with a high molecular weight alkyl or substituted-alkyl chloride or bromide containing 8 to 18 carbon atoms, or an aliphatic halogen-substituted acid, e.g. chloracetic acid, may be used and the resulting naphthylamino-acid condensed with a high molecular weight amine.  An aliphatic halogen-substituted acetal, e.g. chloropropionaldehyde diethylacetal, may be reacted with the naphthylamine, followed by acetal interchange into a polyvinyl acetal by the method of Specification 535,341.  A 1-acetamino-2-substituted-naphthylamine-5,6, or 7-sulphonic acid may be treated with chlorosulphonic acid or PCl5 to form the sulphonyl chloride, a sulphonamide formed with a high molecular weight amine, and the acetamino group hydrolysed.  A 1 - nitro - 2 - substituted - naphthalene - 5,6 or 7-carboxylic acid or 1-nitro-2-naphthoic acid may be treated with PCl5, and the resulting acid chloride reacted with a high molecular weight amine, or polyamine, e.g. octylamine, octadecylamine, cyclohexyl-amime, or amino-cellulose, following which the nitro group is reduced and, if desired, the amino group alkylated. Other reactive groups, e.g. OH, NH2, CHO, thiol, sulphonyl chloride and COOH, may be introduced into the molecule and caused to react to form high molecular weight ethers, amides, esters, substituted amines, sulphides, or sulphones.  a -Naphthylamines referred to are the 2-methyl, 4-chloro-2 methyl, 2-carboxylic acid (and esters and amides thereof), 2-methoxy, 2 - ethoxy, 2 - methoxy - 6 - sulphonic acid, 2-ethoxy-6-sulphonic acid, 2-nitro, 2-chloro, 2-nitro-4-bromo, N-methyl-2-nitro, N-ethyl-2-nitro, 2-methyl-4-bromo, 2-methyl-8-chloro, and 2-nitro-3-chloro compounds and 2 : 21-dinaphthyl-1 : 11-diamine.  Heterocyclic compounds derived by linking up of the 2-substituent are 2 : 3 - dihydro - a  - naphthazole, 1 : 2 - dihydro - b  - naphthathiazole, a -benzcarbazole hexahydride, 8 : 9 : 10 : 11 : 12 : 13-hexhydrobenzphenoxazine and 1 : 2 : 3 : 4-tetrahydro-7 : 8-benzquinoline.  The a -naphthylamines have preferably a lower (1 to 4C) alkyl or alkoxy group in the 2-position.  In example (1), 1-amino-2-methoxynaphthalene-6-sulphonic acid is reacted with p-acetaminophenoxyethyl bromide acetyl, the group hydrolysed and the product condensed with a styrenemaleic anhydride heteropolymer.  1-b -Aminoethylamino-2-methylnaphthalene is prepared by reacting in a closed container under pressure 1 - hydroxy - 2 - methylnaphthalene, water, SO2 and ethylenediamine.  2 : 3-Dihydro-a -naphthazole is prepared by stirring N - b  - chloroethyl - 1 - naphthalene in butanol at 110 DEG  C. for 8 hours and reacting hydrochloride thus formed with sodium carbonate solution.  1 : 2-Dihydro-b -naphthothiazole is prepared in a similar manner to benzthiazoline.  g -8 : 9 : 10 : 11 : 12 : 13-Hexahydrobenzophenoxazine is prepared by condensing 2-hydroxy-1-naphthhydrazine with cyclohexanone.  1 : 2 : 3 : 4-Tetrahydro-7 : 8-benzoquinoline is prepared by heating 1-g -chloropropylaminonaphthalene in butanol at 100 DEG  C. for 10 hours and reacting the hydrochloride thus formed with sodium carbonate solution.  Specifications 2562/13, 133,034, [both in Class 98 (ii)], 397,159, [Group XX], 436,587; 458,400, 465,823, 478,345, 479,838, [all in Group XX], 483,000, 484,698; 487,769, [Group XX], 489,093, 491,958, 491,959, 512,542; 520,528, [Group XX], 541,649; 545,443, [Group XX] 552,009, 554,302, 556,768; 556,858, [Group XX], 562,092, 569,646, and 14656/39 (as open to inspection under Sect. 91) also are referred to.  The Specification as open to inspection under Sect. 91 refers also to the use as couplers of 1 : 2 - dihydro - b  - naphthoxazole and 1 : 2 - dihydro-4-naphtho-(1 : 2-a )-m-oxazine. This subject-matter does not appear in the Specification as accepted.